Refining canadian or similar petroleum-oils



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H. FRASGH. I

REFINING CANADIAN 0R SIMILAR PETROLEUM OILS.

Patented Nov. 29, 1892.

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BUM OILS. N

OR LAB PETROL Patented FIGJII- (No Model.) I

. REFINING CANADIAN No. 487,119.

' UNITED STATES HERMAN mason, or LONDON, o

ANADA, nsstenon To TEE-"SOLAR REFINING COMPANY, OF. OHIO; BEFININGCANADIAN10R:SlMlLARlPET RCLEUM-OILS,

5 .srncmcninolv forming part of Letters Patent No.4 87,1;l9, datedNovember 29,1892.

Application filed February 15, 1888. Serial messiah (no specimens.) 1

- To allwltom it maly concern in the Province of Ontario, Canada, havein- Be it known that I, HERMAN FRASCH, a citi;

zen of-the United States, residing at London,

vented certain new and useful Improvements in the Process of RefiningCanadian and Similar Petroleum-Oils, of which the following Canadian anda similar petroleum'such,for

.'example, as that found at Lima, in Ohio. This oil requires adifierenttreatment from the} ordinary American oil, because of thesulphur a present in these oils in considerable 'proportion, and some,at-least, of r the sulphur com-- specification is a full,- cleanandexact'descrip-- tion;

This'in-vention relates to the treatment of compounds which it containsand which give it its penetrating disagreeable odor and ren-, der itunfit for burning in lamps unless de-' prived of said compounds. Thesulphur-is donsreaty, upwardof one-half of one per centum, (\f of 1%,)mostly in chemical combinapounds are essentially difier'ent from thosewhiclr occur in other oils and-are retained with great tenacity. T-hesepeculiar sulphur,

compounds have received among the workers in the oils of this class thesuggestive name of skunk. To deprive these oils of theirpeculiar'sulphur compounds'or skunk is the object of the presentinvention.

- The large proportionof sulphur will generallyd'istinguish Canadianandsimilar skunks bearing petroleum from'other oils; bill afur- -therdistinction may be found in the nature;

of the sulphurcontaining bodiesthereinl' They give to the oils theproperty of dissolving lead oxide, (litharga) So far as I am aware, nomineral oil, whether undistilled ordistillate other than Canadianorsimilar skunkbearing petroleum possesses this property of dissolvinglitharge. Ordinary petroleumcan be made to dissolve litharge bytheaddition erty-of dissolving lead oxide. On distillation,

odor reappears, and-the oil; will again disfwill removepractically allthe sulphurfexist invention there yet remainsin'said petroleum phur .insuch form or;forms -thata repeated fails. toeliminate it or materiallyto reduce 'spect to the sulphur bodies-thereimsaid bodies. giving-totheskunk-bearing oil peculiar properties, as' hereinbefore mentioned,and being not removable by the refining means in common use, which doremove, the sulphur from -,American petroleum, while at the sametime-means eflicient to remove skunkdo not take out sulphur bodiesremovable by said "refining; means-in common use on American oil,so'that theutility of certain reagents or.

mineral oils is no proofjof an ability to remove the skunk of Canadianand similar petroleum, nor does an ability to remove skunk constituteing the place of the ordinarymeans of desulphurizing oil, r a

Heretofor'e it has'been customary in Canadian refineries (and the sametreatment has been employed in parts of the United States) to take theburning-oil distillate which has been subjected to the actionot'sulphuric acid and washed with water and to treat the same withasolution of plumbate of soda in order to deodorize it,and then to addsulphur in powder in order to restore the color which the plumba'tesolution has turned to a yellow or The malodor also reappears; on'b-urniug and f the lamp-chimneys become smoked. More over, while-thesulphur existing in. the'oil as skunk is not removed byjtreating the oilwith sulphuric -acid and, alkali (which treatment application; of theskunk-removing; process proof of agiven process being capable of tak-vPATENT: OFFICE; 1

' however, of fmebirf rbln which". the lead has been precipitated,as-just described, the maling in Pennsylvania oil) it is also true thatI after the removal of .the skunk from Canadian and similar petroleumby. the present- (now become sweet and incapable of 'dissolv-.ingrz-lead oxide even after redistilla'tion) 'sul;

its proportion, while it can: be-separatedal-- inostjentirely-bjtreatment-with sulphuric acid. .Skunh bearing oil therefore is'radically differfent from other 'mineral oils in r ef modesofitreatmeut in desulphurizing other 1 brown and cause the precipitationof the lead,

leaving the oil above it white and clear. The solution of soda settlesto the bottom. The objections to this old deodorizing process aretwofold: First, an excess of sulphur is liable to be added in the secondstage, which is injurious to the oil, and, secondly, the treat ment isnot thonough, for it does not remove the sulphur compounds or skunk, butonly renders the same inodorous and incapable of further uniting withthe lead oxide of the plumbate solution. On distillation the sulphurcompounds in the oil again become malodorous and the oilis discolored bythe addition of the plumbate of soda solution.

In a priorapplicationfiled February 21 1887, and oflicially seriallynumbered '228,403, (on which Patent No. 378,246 was granted me February21, 1888,) I have described apro' cess not open to these objections forrefiningoil of the Canadian or Lima class by distilling the same withsuitable oxides or compounds mixed with or dissolved in the oil undertreatment. The present invention is, as it were, a supplement to orcomplement of that process. I have discovered that the refractorysulphur compounds or skunk of Canadianaud similar oils are decomposed bythe metallic oxides or compounds without nec essarily having such anoxide or compound dissolved in or mixed with the oil in distillation bysubjecting. the vapors after leaving the liquid oilto the action of asuitable liquid holdingin solution or solution'and suspension one ormore of the said oxides or their com- .pbunds. The vapors may be broughtinto contact in any ordinary or suitable way with the liquid holding insolution or solution and suspension one or more-of the oxides or com--pounds. The vapors may bubble through a body of the liquid, or they maypass through a shower or spray of the same, or they may come in contactwith theliquid in both these or in other .ways.-

In my divisional application, Serial. No. 378,818, filed January 23,1891,,1 have claimedv that process or improvement which consistsgenerallyin subjecting the vapors of skunkcontaining petroleum afterleaving the oil in distillation to the action of suitable oxides orcompounds, for it is possible (although much less effective) to employ.oxides or compounds otherwise than in solution or solution andsuspension in a suitable liquid, and there are advantages incident tothe carrying on of the purification outside the oil in distillationwhich are not restricted to the use of a liquid, as above set forth,although very great and V important special advantages attend such use.

Suitable oxides are those of the more common heavy metals which give uptheir oxygen with comparative readiness,and are generally those ofmetals which form sulphides convertible into oxides by roasting andoxidation. The oxides of lead, bismuth, cadmium, mercury, copper, andsilver are well suited to the purpose, also binoxide of manganese,except for the difliculty of'revivification; but the ferric, stannic,and antimonic oxides, cuprous oxide, and the oxides of nickel, cobalt,and zinc are less energetic and are more useful inconnection with thosefirst mentioned, among which is to be included manganese binoxide, thanwhen used alone. The lower oxides of manganese and the oxides ofpalladium and rhodium may be used. The oxides of manganese are moreuseful when employed in connection with lead oxide than when used alone.7

Suitable compounds are the readily-decomposable oxygen compounds-such,for example, as the carbonates of metals-which give up their oxygen withcomparative "readiness and.the oxygen salts in general of metals whichare precipitated by hydrogen sulphides in acid solutions, such as theinanganates,

chromates,borates, sulphates, and the like of said metals,

Suitable liquids are those of an oily or resinous 'nature,aud especiallythose oily liquids compounds dissolved in or mixed with said liquid. Thevapors from one still mayin fact be passed through the liquid in anotherstill, in which. latter the oil under treatment is mixed with or holdsin solution one or more suitable metallic oxides or compounds. In

plying and maintaining the oxide or compound in excessof the solventcapacity of said liquid, so asto have the solution saturated with,undissolved oxide or compound mixed therewith in solid form, for theoxide is in the most active condition when dissolved, and as thereaction with the sulphur compounds or skunk takes place metal isprecipitated from the solution in chemical combination or from which thevapors have been generated as in proceeding according to thespecification of my aforesaid patent, is improved in respect to therapidity with which it can be carried on by the use in connection withthe metallic oxides or compounds of one or more of the acidhydrocarbons, such as oleic acid, stearic acid, margaric acid,colophonic v acid, (rosin,) and-other fatty or resinous acids. Theacidmay be'mixed with the oxide or compound or be in chemical combinationate, oleate,or the like. The liquid condensed from the vaporswhich'havethoroughly been brought into contact with the oxide orcompound, so as to} give it opportunity to. act

upon all the sulphur compounds or skunk, will stand the plumbate-of-sodatest. I find,

-however, that the condensed liquid or distildate purified from skunk,although it will stand theplumbate-of-soda test, yet containssulphur'compounds, which I believe to be pe-,

culiar to oil treated in this way and which impair the value of the oilby causing a chimney-de'posit when burned in a lamp. These products,like the. similar or identical ones from distilling the oil with the.purifying oxide or compound mixed' 'with or dissolved in" the-same, areessentially difierent from skunk .and are, as I-haveidiscovered,removable by treatment with sulphuric acid, washing with water, andneutralizing, as customary inre- 'fining American-petroleum.

The metallic sulphur compounds which are formed by thereaction with thesulp ht'1r-co1r,- taining impurities .Of-the; v'apors, as above set.forth, can be reviviiied by roasting and oxida tion and these revivifiedresidues can be eIn-L ployed suceessfullyto treat new vapor-sotQanadian. or Lima or similar skunk-bearing oil.

illustrationand example. I

In the drawings,-Figure:1is a sectional view:

of an oil still' andxpurifiersuitablefor,use in carrying the inventioninto efie'ctfi-F-ig. II is .a similar vie'w' of a -slightly-.mcdifiedform ofthe same apparatus,.and Fig. IIIis a-similar view ofanother form-of; apparatus.

Referringito Eigs'I and lLanordil-iarystill A is provided with'a coluninB, whichih'as baf fle-plates or trays and stirrer s,-a s common, orat'leas't known,'.in various chemical arts. In Fig. I the ,ba file-plates 2am in the fOI'm' :0f circular disks, which. are mountedhorizontally on an upright central shaft 3,.and the baflie plates4 areintheform of rings fastened to the walls of the colu mnB andprojectingiiiwa'rd between the disk plates 2. In Fig. 11 the trays 5 arefastened to the walls of thecolum-n, and.

the openings for the passage of the vapors are formed at the oppositesides of alternate trays; and the shaft 6 is provided with stirrerswhich 7 dip intothe trays. In both figuresthe top of the still A isconue'cted'by a vapor-pipe 7 with the' column B, and at the top of thelatterithere.

is; a pipe '8 for conveying the ,purified vapors the column. .The stillA' and the column B to the condenser. (Not shown). A pipe 9 leads fromthe base of the column B to the pump-C and a pipe 10 from -.the saidpump 0 to the top 'of said column. The shafts 3 and 6 are rotated bybevel-gear, and the column .B, which restson a pillar 11, is heatedby'the products of combustion from, the fire-chamber D under; the stillon-their way to the chimney E. The column B should be of such size as tobring the vapors sutficientlyinto contact with the purifying material.If the still be. such as commonly used to' distill-a charge ofijonehundred barrels of'oil, the column B maybe, say, ten feet high andlfourfeet in diameter, with the baflierplates or trays about six inchesapart. p In operation the still ,is charged-with, say, onehundredbarrels of oil composed of, say, fifteen .pei' centumof heavy oilof from 36 to 398 Baum, and the remainder burning-oil distillate boilingat 2129f Fahrenheit orov'er.

The column is suppliedjwith, s y, five b'arrels of heavy impureOrskunk-bearing (Danadian or similar. oil mixed with, say,,one'baroxide,(litharge,).'onethousand poundsof'cm rel. of resin, -fi-ve hundredpounds of pln'rnbic' pricoxide,.-(black oxide,)j and one thousandpoundsof plaster-'of-paris, the oxides and plaster being finely .g'round andbolted. 'Therosin and part of. the oxides dissolve in. theoil andtherestot theoxidds' and plaster are kept in the bafile plates or trays,which trays'become -filled, and collects-in the bottom of the columnsuspension therein.- The oil,.with-the"matter. ,insolution andsuspension therein, flows over B. After or before the oil is introducedthe 'pum'p is'started which drawsfpfi through the pipe 9, the oilholding the oxide in solution and suspensionwherein"and returns. it tothe top of,-th e column B through the-pipe 10-5 m.

shaft. 3 in the column 'is also rotated; The

uid and solids 'ofi onto the rings 4,'from which they descend to thenext, disk by gravity, the flow of the'lijq-uids being'sufiicienttofsweep.

away the solid particles; but, if desired, me-. 'chanical devices orscrapers could be em-.-

ployed to sweepior scrape thesurfaces'of the being charged'and the pump0 and shaft 3 (or 6-). incol'ulnn B being started, the still A rotationof the disks 2,-- Fig I, throws th etliq r I 5 ratu s,wherein gasesorvapors are to be thought 3 I cjles in suspension therein. The rotationof' in the bottom'of thecolumn B by means of andcolumn B are heated, theformer to -evaporate the burning-oil therein and'thelatter to prevent'ordiminish th'econdensation of .the vapors from the still. The vapors passthrough the pipe 7 into 'the lower part of column Bf.

through which they then; pass upward, and are in their'passage broughtinto intimate con.-

tact with the liquid holding the oxides in solution and suspension, saidliquid, with the oxides, flowing in the opposite direction over thebattle-plates or trays and falling from one to the other through therising vapors. The vapors escape by the pipe 8 to the condenser. Thepassage of the vapors through or over the liquid enables the oxides toact on the skunk in said vapors with the formation of metallic sulphurcompounds which remain in the liquid and certain new bodies which passoff with the vapors. A constant stream of the oil having the oxidesdissolved and suspended therein is introduced at the top of the column Band drawn ed at the base. The liquid drawn oii is returned to thecolumn, the whole or a portion of the precipitated or solid matter insuspension being removed and replaced by fresh oxides at each round orfrom time to time. As the metal of the oxides in solution .combines withthe sulphur of the skunk and.

becomes insoluble fresh oxide enters the solution, the same beingsupplied from the mat- V ter in suspension. The still is or may besupdensed vapors must be taken care of eitherby returning them to thestill or otherwise. If solid matter is allowed, in the still either byentering in that state from the column B or by precipitation in thestill, the latter should be provided with an agitator to keep it fromsettling.

' The plumbic or the cupric oxide could .be used alone-say thirty-threehundred pounds of plumbic oxide or twelve hundred pounds of cupricoxide,-or one or both could be re placed by or used in connection withanother or others of the specified agents. The plaster and therosin maybe omitted.

It is not necessary to use heavy oil in the puritier'column, althoughsuch oil is preferable to a lighter petroleum, because it does notvolatilize in the column; nor need the oil inthe said purifier-column.contain the sulphur compounds which enable it to dissolve the oxides,for the solubility of the oxides might be seen red by other means-suchas the use of a fat acid-or the oxides, if simplyheld in suspension inan oily menstrum not originally a solvent of the oxides,willbecomedissolved by reason of theskunk brought over by the vaporsfrom the still; nor need petroleum be used at all, as rosin alone wouldanswer.

According to another plan of working (see Fig. III) the still A isprovided inside with a large pipe E, which communicates with theinterior of the still through the opening 15 and also with a smallcolumn G, such as used in rectifying alcohol on top of the still, andwith a small vessel or receiver 16 inside the still. A steam-injector orsteam-jet aspirator and compressor H sucks the vapors from the upperpart of the still A and forces them through the pipe F into the bottomof the column G. The injector H also forces into the pipe F and amongthe vapors therein the purifying oxide or compound finely divided anddissolved in or mixed with an oilyliquid. As shown, there is a reservoirK, provided with a stirrer 17, from which the injector H draws a supplyof oxide or compound in suspension or in solution and suspension in theoily liquid. More or less of the oxide is forced with the vapors intothe column. What does not so pass is carried into the small vessel orreceiver 16, the object of which is to keep the sediment from the bottomof the still. This material could be allowed to run into the still; butin that case the latter should have an agitator, or it could bedischarged outside of the still to be returned or otherwise disposed of.The column G has an overflow at thebottom, which discharges into thereceiver 16. The oil or condensed vapor in this receiver is volatilizedagain and passes in vapor form into the pipe F and then into the columnG. The large pipe F may have an opening into the vaporspace at each end,so as to circulate the vapors through the pipe as well as force theminto the column G. The steam-jet to force the vapors could be used inthe arrangements described with reference to Figs. I and II. Other modesof bringing the vapors into contact with the purifying agents have beenindicated in the first part of this specification.

The larger the proportion of skunk in the oil the more thoroughly shouldthe vapors be brought into contact with the purifying agents, and if theprocess is carried on by batches-that is, without a constant renewal ofthe oxide or compoundcare should be taken to have the amount ofpurifying agent larger than necessary to decompose all the skunk. Theweight of oxides given would be ample for one hundred barrels of oilcontaining about one-half of one per centum of sulphur.

The vapors from the purifying apparatus are received in a condenser (notshown) andthe condensed liquid is washed with sulpliuric acid, or it maybe used without such washing.

The solid sulphur-containing residue from the above operation or from ananalogous operation is roasted and oxidated and after grinding andbolting is used like fresh oxide.

In order to revivify the purifying agent or agents, the solid residue isor ordinarily would be so arated by straining or otherwise from the o'lyor resinous liquid with which it is mixed'and is then thrown into thefront part of a roastingrfurnace a portion ata time and ignited. The oiladhering, in connection with the sulphur and metal, furnishes all theheat necessary for roasting. The air will supply the oxygen, so as toeffect the revivification at one operation. As each fresh portion isadded, the portions previously introduced are transferred to thefurnace.

pushed back until the,whole charge has been The mass becomes red-hot andis-thoroughly roasted and oxidated. The due division of the powder andits composition insure a perfect and quick roasting. It is stirred untilbelow'red heat and is. then discharged to be reground for use again. Theoily or resinous liquid is used again with fresh purifying agents.

I do not claim herein the apparatus described. It forms the subject ofmy application, Serial No. 289,746, filed November 1, 1888 nor doIclaimherein the revivification of the residue of the revivifiedresidues, as such matter forms the subject of my application, SerialNo;12 ,84,830, filed September 7, 1888; but the use-of the revivifiedresidues, as herein described, is included in the present invention. g

The expression vaporizing the oil and subjectingthe sameto the action asemployed in the second, fourth, and-fifth clauses of claims following isintended to apply' as well to the action which occurs within the oilwhen the latteris distilled with the purifying agent dissolved thereinor mixed therewith as to an action on the oil vapors after they havebeen given on: from the body of the liquid oil undergoing distillation.

The advantages which are secured by the carrying on of the process ofpurification of the vapors of distillation outside the oil in or fromwhich .the same have been generated are not confined to the use of aliquid solvent,

but toja greater or less degree extend to the use of the oxides in adrystate, and thisgeneral feature of my invention-namely, the carrying onof the purification outside theliquid in ,or from which the vapors havebeen generated-is made the subject of. my divisional application, SerialNo. 378,818, filed January 23, 1891.

I claim herein as my invention or discovery 1. The process of removingthe sulphur compound termed skunk from Canadian and similaripetroleum,which consists in vaporizing the oil and subjecting the vapors afterthey are given on? from thebody of the oil to the action of' an oily orresinous liquid holding in solutioh or solution and'suspension one ormore metallic oxides soluble in said oil, including the decomposablecompounds of such oxides, and condensing such purified vapors,substantially as described.

2. The process of removing the sulphur compound termed skunk fromCanadian and similar petroleum, which consists .in vaporizing the oiland subjecting the same to the action of a solution in an oily orresinous liquid composed of one or more metallic oxides soluble in saidoil, including the decomposable compounds of such oxides, andmaintaining an excess of the soluble but as yet undissolved purifyingagent in suspension in said solution, whereby the said liquid is keptsaturated, substantially as described.

3. The process of removing the sulphur compound termed skunk fromCanadian and similar petroleum, which consists in vaporizing the oil,subjecting the vapors after they are given off from the body of theoil-to the action of films, showers, or sprays of an oily or resinousliquid holding in solution or solution'and suspension one or moremetallic oxides soluble in said oil, including the decomposablecompounds of such oxides, and condensing such purified vapors,substantially as described.

4. The process of removing the sulphur compoundtermed skunk fromCanadian and similar petroleum, which consists in vaporizing the oil andsubjecting the same to the action of purifying material, composed of orcontaining one or more of the metallic oxides soluble in saidoil,including their decomposable compounds, and one or more fatty orresinous acids, such as oleic, stearic, margaric, colophonic acids,substantially as described.

5. The process of removing the sulphur compound termed skunk fromCanadian and similar petroleum, wh'ich consists in va-- porizing the oiland subjectingthe vapors to the action of a metallic 'oleate,colophonate,

-or other metallic salt of a fatty or resinous acid, substantially asdescribed.

- 6. The process *of removing the sulphur compound termed skunk fromCanadian and similar petroleum, which consists in vaporizing the oil andsubjecting the vapors after they are given off from the body of the oilto the-action of an oily or resinous liquid containing said sulphurcompound termed ,fskunk, and one or more metallic oxides soluble inskunk-bearing oil, including the decomposable compounds of such oxides,and condensing such purified vapors,substan tially as described. i

7: Theprocess of removing the sulphur compound termed skunk fromCanadian andsimilar petroleum, which consists in vaporizing the oil andsubjecting the vapors after they are given off from the body of the oilto the action of an oily or resinous liquid holding in solution orsolution and suspension one or more metallic oxides soluble in said oil,including their decomposable compounds, condensing such purified vapors,and washing the condensed liquid with sulphuric acid, substantially asdescribed.

In testimony whereof I have signed this specification in the presence oftwo witnesses.

' HERMAN FRASCH.

Witnesses:

J. W. VAN DYKE, W. B. RICHIE.

' It is hereby certified that in Letters Patent No. 487,119 grantedNovember 29, 1892, upon the application of Herman Frasch, of London,Oanada, for an improvement in Refining Canadian or Similar PetroleumOils, an error appears in the printed specification requiring correctionas follows In line 61, page 5, the word composed should be stricken out;and that the Letters Patent should be read with this correction thereinthat the same may conform to the record of l the case in the PatentOffice. I

Signed, oountersigned, and sealed this 24th day of January, 1893.

[SEAL] CYRUS BUSSEY,

I Assistant Secretary of the Interior, Oountersigned W; E, SIMONDS,

Commissioner of Patents.

